This invention relates to an agrochemical composition and in particular to an agrochemical composition containing an activity-enhancing adjuvant.
An agrochemical is generally used with an adjuvant or combination of adjuvants to provide optimum biological activity. Much has been published on the selection of adjuvants to achieve particular effects with individual agrochemicals and classes of agrochemical. In general it has been assumed that activity-enhancement results from surfactant properties of the adjuvant and most such activity-enhancing adjuvants are surfactants in that they contain within the molecule both a hydrophobic portion and a-lypophobic-portion. We have now found that a class of alkoxylated amines provides excellent activity enhancement when used in an agrochemical formulation. Surprisingly certain members of the class have either no surfactant properties or low surfactant properties. Furthermore, unlike many surfactants used as conventional agrochemical adjuvants, the alkoxylated amines of the present invention generally exhibit an exceptionally low toxicological profile and in particular excellent ecotoxicological characteristics and provide compositions which are especially benign to the environment. It is exceptional to find adjuvants which combine a high level of activity enhancement with low toxicity.
According to the present invention there is provided an agrochemical composition comprising an agrochemical active ingredient and an adjuvant of formula (I) and salts thereof
Xxe2x80x94(R3O)axe2x80x94R4xe2x80x94NR2R1xe2x80x83xe2x80x83(I)
wherein R1 and R2 are independently hydrogen or a lower alkyl group or a group Xxe2x80x2xe2x80x94(R3xe2x80x2O)axe2x80x2xe2x80x94R4xe2x80x2xe2x80x94 wherein R3xe2x80x2 and R4xe2x80x2 respectively may take any of the values of R3 and R4 as hereinafter defined and wherein Xxe2x80x2 is xe2x80x94OH or a lower alkoxy group containing from 1 to 6 carbon atoms and axe2x80x2 is from 0 to 400
R3O is an ethoxy, propoxy or butoxy group or a random or block mixture thereof,
R4 is a linear or branched chain alkylene bridging group containing from 1 to 4 carbon atoms, X is
(IA) xe2x80x94OH or a lower alkoxy group containing from 1 to 6 carbon atoms
or X is
(IB) a group R5R6Nxe2x80x94 or R5R6Nxe2x80x94R7xe2x80x94
wherein R5 and R6 are independently hydrogen or a lower alkyl group or a group Xxe2x80x2xe2x80x94(R3xe2x80x2O)axe2x80x2xe2x80x94R4xe2x80x2xe2x80x94 as hereinbefore defined wherein Xxe2x80x2 is xe2x80x94OH or a lower alkoxy group containing from 1 to 6 carbon atoms,
and R7 is a linear or branched chain alkylene bridging group containing from 1 to 4 carbon atoms
or X is
(IC) a group 
wherein R10, R11, R14 and R15 are independently hydrogen or a lower alkyl group or a group Xxe2x80x2xe2x80x94(R3xe2x80x2O)axe2x80x2xe2x80x94R4xe2x80x2xe2x80x94 as hereinbefore defined wherein Xxe2x80x2 is xe2x80x94OH or a lower alkoxy group containing from 1 to 6 carbon atoms;
and R8 and R12, are independently alkyl groups containing from 1 to 4 carbon atoms and R9 and R13 and R21 are independently a linear or branched chain alkylene bridging group containing from 1to 6 carbon atoms, R16, R17, R18, R19 and R20 are independently hydrogen or a lower alkyl group and d is 0 or 1
and wherein a, is from 1 to 400 or if X is of formula IC, the sum of a, b and c is from 3 to 400.
A considerable number of salts of the compound of formula (I) suitable for use in agrochemical applications will occur to one skilled in the art. Examples of salts include phosphate, sulphate, carboxylate, acetate, formate and chloride although many other suitable salts will occur to one skilled in the art. Alternatively the compound of formula (I) may form a salt with an acidic agrochemical such as glyphosate. Salts of the compound of formula (I) can also be prepared from acidic surfactants, for example optionally ethoxylated alkyl or alkylene ester derivatives of phosphoric acid or phosphonic acid, or optionally ethoxylated alkyl or alkylene carboxylic acids or sulphonic acids. It will be appreciated that where more than one amine functionality is present in the compound of formula (I) or the relevant acid has more than one functional group, the option for different salt stoichiometries and mixed salts exists and all such variations are included herein.
As used herein, the term lower alkyl means a linear or branched chain primary or secondary alkyl group containing from 1 to 6 carbon atoms. Preferred lower alkyl groups contain from 1 to 4 carbon atoms, and methyl, ethyl and propyl or isopropyl groups are especially preferred.
R1, R2, R5, R6, R10, R11, R14 and R15 are preferably methyl or hydrogen. Hydrogen is especially preferred.
Thus it is preferred that in a compound of formula (I):xe2x80x94
X is xe2x80x94OH or a lower alkoxy group containing from 1 to 4 carbon atoms or
X is R5R6Nxe2x80x94 wherein R5 and R6 are hydrogen or a lower alkyl group containing from 1 to 4 carbon atoms or
X is a group of formula ICxe2x80x2
wherein R8O and R12O are independently ethoxy, or propoxy, in particular isopropoxy, or a random or block mixture thereof, R9 and R13 are independently a linear or branched chain alkylene bridging group containing 2 or 3 carbon atoms and R21 is a linear or branched chain alkylene bridging group containing from 1 to 3 carbon atoms, R18 is hydrogen or lower alkyl containing from 1 to 4 carbon atoms and d is 0 or 1,
R1 and R2 are independently hydrogen or a lower alkyl group containing from 1 to 4 carbon atoms, R3O is ethoxy, or propoxy, in particular isopropoxy, or a random or block mixture thereof, R4 is a linear or branched chain alkylene bridging group containing 2 or 3 carbon atoms and a is from 1 to 400 or if X is of formula ICxe2x80x2, the sum of a, b and c is from 3 to 400.
The compounds for use in the composition of the present invention are alkoxylated monoamines (X is of Formula IA), diamines (X is of Formula IB) or triamines (X is of Formula IC). Alkoxylation typically takes place to introduce ethoxy groups or propoxy groups, although butoxy groups may sometimes also be used. The propoxy group is preferably an isopropoxy group, xe2x80x94OCH2xe2x80x94CH(CH3)xe2x80x94. Mixed alkoxylation may also take place to introduce for example both ethoxy and propoxy or butoxy groups which may be present as a mixture in either random or block arrangement. Thus each of xe2x80x94(OR3)axe2x80x94, xe2x80x94(OR8)bxe2x80x94 and xe2x80x94(OR12)c)xe2x80x94 in the above formulae independently represent alkoxy groups, for example ethoxy and propoxy groups or a mixture thereof. Thus the definition of group xe2x80x94(OR3)a for example includes a group
xe2x80x94(OC2H4xe2x80x94)xxe2x80x94(OCH2xe2x80x94CH(CH3)xe2x80x94)y
wherein a is represented by the sum of x and y. Other combinations of for example ethoxy propoxy and butyoxy groups in any desired order are similarly included in the definition of xe2x80x94(OR3)axe2x80x94, xe2x80x94(OR8)bxe2x80x94 and xe2x80x94(OR12)cxe2x80x94 respectively.
The process of alkoxylation may produce a mixture of products having different degrees of alkoxylation. Thus the values of a, b, c and axe2x80x2 represent an average degree of alkoxylation over the product as a whole. Preferred values of a, b, and c, respectively are from 1 to 100, for example from 1 to 50 and especially from 1 to 30 . Thus when X in formula (I) is of formula IC, the sum of a+b+c is preferably from 3 to 90. In the group Xxe2x80x2xe2x80x94(R3xe2x80x2O)axe2x80x2xe2x80x94R4xe2x80x2xe2x80x94 if present, axe2x80x2 is preferably from 0 to 50 and especially from 0 to 30.
An especially preferred alkoxylated monoamine (wherein X is of formula IA) for use in the present invention has the formula II wherein X is methoxy, xe2x80x94(R3Oxe2x80x94)a represents a mixture of ethoxy and propoxy groups R4 represents a propylene bridging group.
CH3xe2x80x94Oxe2x80x94(xe2x80x94CH2CH2Oxe2x80x94)xxe2x80x94(xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94Oxe2x80x94)yxe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94NH2xe2x80x83xe2x80x83(II)
The average degree of ethoxylation (x) may vary from 0 to about 45 or more preferably from 0 to about 40, for example from 0 to about 20 and the average degree of propoxylation (y) may vary from 0 to about 90 and more preferably from about 1 to about 35, for example from about 2 to about 30, provided that x and y are not both 0 at the same time. Products are commercially available wherein x is about 1 and y is about 9; x is about 19 and y is about 3, x is about 6 and y is about 29 and x is about 32 and y is about 10. As specific examples of commercially available products there may be mentioned JEFFAMINE M600 (JEFFAMINE is a trade mark of Huntsman Limited) having an approximate molecular weight of 600 and a propoxy to ethoxy ratio of 9 to 1, JEFFAMINE M1000 having an approximate molecular weight of 1000 and a propoxy to ethoxy ratio of 3 to 19, JEFFAMINE M2005 having an approximate molecular weight of 2000 and a propoxy to ethoxy ratio of 29 to 6 and JEFFAMINE M2070 having an approximate molecular weight of 2000 and a propoxy to ethoxy ratio of 10 to 32.
Also included in the scope of the present invention is
(i) diethylene glycolamine wherein in Formula I, X is OH, (R3O) is ethoxy, a is 1 and R4 is an ethylene bridging group and R1 and R2 are hydrogen:
HOxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2CH2xe2x80x94NH2 and
(ii) a compound of formula 
wherein in Formula I, X is xe2x80x94OH, R3 and R4 are isopropyl, R1 and R2 are Xxe2x80x2xe2x80x94(R3xe2x80x2O)axe2x80x2xe2x80x94R4xe2x80x2xe2x80x94, Xxe2x80x2 is xe2x80x94OH, R3xe2x80x2 and R4xe2x80x2 are ethyl and x, y and z respectively take any of the values defined for a or axe2x80x2 as the case may be and
(iii) a compound of formula 
wherein in Formula I, X is R5R6Nxe2x80x94, R3 and R4 are isopropyl, R1, R2, R5 and R6 are Xxe2x80x2xe2x80x94(R3xe2x80x2O)axe2x80x2xe2x80x94R4xe2x80x2xe2x80x94, Xxe2x80x2 is xe2x80x94OH, R3xe2x80x2 and R4xe2x80x2 are ethyl and v, w, x, y and z respectively take any of the values defined for a or a as the case may be.
Also included in the scope of the present invention is
tris 2-(2-methoxyethoxy)ethylamine wherein in formula I, X is OCH3, (R3O) is ethoxy, a is 1 and R4 is an ethylene bridging group and wherein R1 and R2 are each a group xe2x80x94R4xe2x80x2xe2x80x94(OR3xe2x80x2)axe2x80x2xe2x80x94Xxe2x80x2 wherein (R3xe2x80x2O) is ethoxy, axe2x80x2 is 1, R4xe2x80x2 is an ethylene bridging group and Xxe2x80x2 is OCH3.
An especially preferred propoxylated diamine (wherein X is of formula IB) for use in the present invention has the formula III wherein X is a group H2Nxe2x80x94, xe2x80x94(R3Oxe2x80x94)a represents propoxy groups R4 represents a propoxy bridging group:
H2Nxe2x80x94(CH(CH3)xe2x80x94CH2xe2x80x94O)wxe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94NH2xe2x80x83xe2x80x83(III)
wherein w is an average of from about 1 to about 80. Products are commercially available wherein w is an average of about 2.6, 5.6, 33.1 and 68. As Examples of commercially available products of formula III, there may be mentioned JEFFAMINE D230 having an approximate molecular weight of 230 and a value of w of about 2.6, JEFFAMINE D400 having an approximate molecular weight of 400 and a value of w of about 5.6, JEFFAMINE D2000 having an approximate molecular weight of 2000 and a value of w of about 33.1, and JEFFAMINE D4000 having an approximate molecular weight of 4000 and a value of w of about 68. An especially preferred value for w is from about 2 to about 35, for example from about 2 to about 30.
An alternative diamine (wherein X is of formula 1B) having a mixture of ethoxylation and propoxylation for use in the present invention has the formula IV wherein X is a group H2Nxe2x80x94, xe2x80x94(R3Oxe2x80x94)a represents a mixture of ethoxy and propoxy groups R1 and R2 are hydrogen and R4 represents a propylene bridging group:
H2Nxe2x80x94(CH(CH3)xe2x80x94CH2xe2x80x94O)rxe2x80x94(CH2CH2xe2x80x94O)sxe2x80x94(CH2xe2x80x94CH(CH3)xe2x80x94Oxe2x80x94)txe2x80x94CH2xe2x80x94CH(CH3)NH2xe2x80x83xe2x80x83(IV)
wherein the sum of r+t (total propoxy content) is an average of from 1 to 20 propoxy groups, for example from about 1 to 10 propoxy units and s is an average of from 2 to 50 for example from 5 to 50 ethoxy units. Commercial products are available wherein the sum of r+t is about 3.6 and s represents an average of about 9, or 15.5 respectively or wherein r+t is about 6 and s represents an average of about 38.7. As examples of commercially available products of formula (IV) there may be mentioned JEFFAMINE ED 600 having an approximate molecular weight of 600 and an propoxy to ethoxy ratio of 3.6 to 9, JEFFAMINE ED 900 having an approximate molecular weight of 900and an propoxy to ethoxy ratio of 3.6 to 15.5 and JEFFAMINE ED 2003 having an approximate molecular weight of 2000 and an propoxy to ethoxy ratio of 6.0 to 38.7. It is especially preferred that the value of (r+t) is from about 2 to about 15 and s is from about 3 to about 20.
An especially preferred propoxylated triamine (wherein X is formula IC) has the formula (V) 
wherein the sum of d+e+f is an average of from about 5 to 90 and R22 is hydrogen or lower alkyl containing 1 to 4 carbon atoms such as methyl or ethyl, R2l is a linear or branched chain alkylene bridging group containing from 1 to 3 carbon atoms and d is 0 or 1. Products are available commercially wherein the sum of d+e+f is about 5.6, about 50 and about 85 respectively. Thus as examples of commercially available products of formula (V) there may be mentioned JEFAMINE T403 having an approximate molecular weight of 440 and a value of d+e+f (total propoxy content) of 5.6, JEFAMINE T3000 having an approximate molecular weight of 3000 and a value of d+e+f (total propoxy content) of 50 and JEFAMINE T5000 having an approximate molecular weight of 5000 and a value of d+e+f (total propoxy content) of 85.
We have found that the activity enhancing effect of the adjuvants in the composition of the present invention is particularly and surprisingly marked when the agrochemical active ingredient is water-soluble. The agrochemical for use in the composition of the present invention is preferably a water-soluble electrolyte such as an agrochemical salt and in particular a herbicidally active agrochemical salt for example a salt of glyphosate, paraqua or fomesafen. Typical of the commonly available salts of glyphosate are the isopropylamine, trimethylsulphonium, sodium, potassium, ammonium, and ethanolamine salts. Paraquat is generally sold in the form of paraquat dichloride. Fomesafen is generally formulated as the sodium salt.
The proportion of adjuvant of formula (I) to agrochemical, for example glyphosate (expressed as the acid) may vary within wide ranges depending on the desired level of activation. Typically the proportion of adjuvant of formula (I) to agrochemical will be from 1:40 to 3:1 for example from 1:20 to 3:1 by weight and especially from 1:10 to 1:1 by weight.
The compositions of the present invention may be used on their own but are preferably used in the form of a composition containing a carrier comprising a solid or liquid diluent.
Compositions of the invention include both dilute compositions, which are ready for immediate use, and concentrated compositions, which require to be diluted before use, usually with water. The concentration of the composition will depend on the nature of the active ingredient. Typically, and especially for example if the active ingredient is a herbicide, the compositions contain from 0.01% to 90% by weight of the active ingredient. Dilute compositions ready for use preferably contain from 0.01 to 2% of active ingredient, while concentrated compositions may contain from 20 to 90% of active ingredient, although from 20 to 70 is usually preferred.
The solid compositions may be in the form of granules, or dusting powders wherein the active ingredient and adjuvant are mixed with a finely divided solid diluent, e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller""s earth and gypsum. In some instances, and in particular when the active ingredient is glyphosate, inorganic salts such as ammonium sulphate may be used both as adjuvant and solid support. They may also be in the form of dispersible powders or grains, comprising a wetting agent to facilitate the dispersion of the powder or grains in liquid. Solid compositions in the form of a powder may be applied as foliar dusts.
The rate of application of the compositions of the invention will depend on a number of factors depending in particular on the nature of the active ingredient. When the active ingredient is a herbicide, such factors include, the compound chosen for use, the identity of the plants whose growth is to be inhibited, the formulations selected for use and whether the compound is to be applied for foliage or root uptake. As a general guide, however, an application rate of from 0.001 to 20 kilograms active ingredient per hectare is suitable while from 0.025 to 10 kilograms per hectare may be preferred.
The adjuvant of formula (I) or a mixture of different adjuvants of formula (I) may be used as the sole adjuvant to enhance the biological activity or physical properties of the agrochemical or may alternatively be used in conjunction with one or more additional adjuvants. The adjuvant of formula (I) may for example be combined with cationic surfactants, anionic surfactants, amphoteric surfactants or non-ionic surfactants. Such surfactants are well known in the art but as surfactants which are particularly well suited to be combined with an adjuvant of formula (I) there may be mentioned alkyl glycosides (mono and poly), alcohol ethoxylates, alkyl phenol ethoxylates, alkyl ester ethoxylates, sorbitan ester ethoxylates, siloxane ethoxylates, acetylenic diol ethoxylates, optionally alkoxylated tertiary or quaternary alkyl amines, optionally alkoxylated alkyl amine oxides, alkyl betaines optionally alkoxylated alkyl phosphate esters and sucrose alkyl esters. The adjuvant of formula (I) may also be combined with other activity-enhancing adjuvants, for example ammonium sulphate, urea or humectants, such as glycerol, polyethylene glycol, sorbitol, ethylene glycol, propylene glycol and lactate salts.
Certain of the adjuvants for use in the composition of the present invention have surprisingly low surface activity (high surface tension) as compared with conventional agrochemical adjuvants. These adjuvants with low surface activity generally exhibit a more favourable toxicological profile. Surface tension of the adjuvants for use in the present invention was measured as a 0.2% w/v solution in deionised water adjusted to pH 4 with hydrochloric acid at 20xc2x0 C., and preferred adjuvants such as JEFFAMINE ED600 ED900 and D400 have a surface tension measured by this method of greater than 50 mNmxe2x88x921 as compared with AGRIMUL PG2067 alkylpolyglycoside which has a surface tension measured by this method of 28 mNmxe2x88x921. Adjuvants having a surface tension of less than 50 mNmxe2x88x921 also give excellent results and JEFFAMINE D2000 for example having a surface tension measured by this method of 42 mNmxe2x88x921 may even provide advantages on certain weed species as discussed below.
Compositions of the present invention generally exhibit excellent low-foaming properties when the composition is incorporated in the spray tank and during transportation and spraying.
When the active ingredient is a herbicide and in particular a water-soluble herbicide, adjuvants of formula (I) generally provide excellent and effective enhancement of activity in respect of most important weed species encountered in the field. Enhancement may however be less marked on certain xe2x80x9cdifficultxe2x80x9d weed species. We have found that the use of a mixture of an adjuvant of formula (I) with a surfactant and in particular with an alkylpolyglycoside surfactant may provide excellent enhancement of activity both against normal weed species and against xe2x80x9cdifficultxe2x80x9d species. Indeed in certain circumstances synergy may be observed and greater enhancement of control of xe2x80x9cdifficultxe2x80x9d species may be obtained than when using either the adjuvant of formula (I) or the alkylpolyglycoside alone. The ratio of the adjuvant of formula (I) to the alkylglycoside is preferably from 1:40 to 4:1, for example 1:20 to 4:1, especially from 1:6 to 2:1 and most preferably about 1 to 1.
When the active ingredient is a herbicide, the invention provides, in a further aspect, a process for severely damaging or killing unwanted plants, which process comprises applying to the plants, or to the growth medium of the plants, a herbicidally effective amount of a composition as hereinbefore defined.
The invention is illustrated by the following Examples in which all parts and percentages are by weight unless otherwise stated.